CN106146777A - A kind of Biodegradable Shape-Memory Polyurethane material and its preparation method and application - Google Patents
A kind of Biodegradable Shape-Memory Polyurethane material and its preparation method and application Download PDFInfo
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- CN106146777A CN106146777A CN201610254715.9A CN201610254715A CN106146777A CN 106146777 A CN106146777 A CN 106146777A CN 201610254715 A CN201610254715 A CN 201610254715A CN 106146777 A CN106146777 A CN 106146777A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/16—Materials with shape-memory or superelastic properties
Abstract
The invention belongs to polymer science technical field, be specially a kind of Biodegradable Shape-Memory Polyurethane material and preparation method and application.The present invention, with cladodification or linear polylactic acid base aliphatic polyester and polyisocyanates as raw material, prepares line style or three-dimensional netted Biodegradable Shape-Memory Polyurethane material by solution polymerization process.This shape-memory material deformation ratio is about 300%, and shape fixed rate is 97 100%, and shape recovery rate is 95 100%.It is big that material of the present invention has deformation recovery power, and recovery temperature is low, remembers reproducible advantage, has the advantage of biocompatibility and biological degradability simultaneously.By regulation cladodification or the chemical constitution of linear polylactic acid base aliphatic polyester, recovery temperature can be controlled near human body temperature, and the size of scalable restoring force, implant field of medical materials at Minimally Invasive Surgery and human body and have broad application prospects.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of Biodegradable Shape-Memory Polyurethane material and
Preparation method and application.
Background technology
Shape memory is the intellectual material of a class stimuli responsive type.It can change with sensing external environment (as light, temperature,
Electricity, magnetic etc.) stimulation, and make certain response, its mechanical property parameters (such as size, position, shape etc.) be adjusted,
Thus recover to original form.
The discovery of shape-memory material originates from marmem, and as far back as 1963, scientist found that Ni-Ti alloy
At Room Temperature Deformation, again can recover to original shape after heating, shape-memory material causes the world and extensively sends out concern subsequently.At present
Till, it has been found that shape-memory material in addition to metal, also have pottery, polymer, gel etc..Wherein shape-memory polymer
(Shape-memory Polymer is called for short SMP), because the performance of its excellence, is paid close attention to by the most widely.Remember with shape
Recalling alloy to compare, SMP has that light weight is inexpensive, deformation quantity big, be prone to the advantages such as processing, shape memory temperature wide ranges, is weaving
The fields such as clothing, medical apparatus and instruments, Aero-Space.
Shape memory high molecule material, according to its shape memory mechanism, can be roughly divided into thermotropic SMP, electroluminescent type SMP, light
Cause type SMP and chemical co-ordination type SMP.In numerous shape memory high molecule materials, thermic induction type SMP is due to raw material sources
Abundant, deformation recovery condition is prone to executions, performance range of choice width, the range advantage such as extensively, becomes shape memory high molecule
The research emphasis of material.At present, study more thermotropic SMP mainly include trans-polyisoprene (ZL02136921.6),
Polyethylene (ZL02133014.X), polycaprolactone (ZL200410010734.4), polyurethane resin (ZL200610043121.X)
And polylactic acid (ZL200410013749.6) etc..Wherein, shape memory polyurethane owing to having that against weather is good, shock resistance is good,
Repeat the advantages such as deformation effects is good, receive scientist's extensive concern.But most of polyurethane materials cannot drop in nature
Solve and recycle difficulty.Polylactic acid base shape memory polyurethane, in addition to possessing good shape-memory properties, also has concurrently good
Biocompatibility and biodegradability, widened the polyurethane material range of application in biologic medical field.
Summary of the invention
Present invention aims to degradation property and poor biocompatibility that existing shape memory polyurethane exists
Defect, it is provided that a kind of Biodegradable Shape-Memory Polyurethane material and its preparation method and application.
The Biodegradable Shape-Memory Polyurethane material that the present invention provides, is based on line style or cladodification polylactic acid base aliphatic poly
Ester, its shape recovery rate is high, and recovery temperature can be controlled by by the chemical constitution of regulation polyester, thus is reduced to close to body
Temperature.It is suitable for bio-medical material.
The purpose of the present invention can be achieved through the following technical solutions:
The Biodegradable Shape-Memory Polyurethane material that the present invention provides, for one based on linear or cladodification polylactic acid base aliphatic poly
The shape memory polyurethane of ester, is thermal response-type, Biodegradable shape-memory material；This material is with polylactic acid base aliphatic poly
The flexible molecule chain of ester be can anti-phase, the carbamate formed with the alcoholic extract hydroxyl group of polyisocyanates and polyester, copolymer crystallization
And chemical crosslinking point is fixing phase, its structural formula is:
Wherein, A is polyhydric alcohol, and B is polylactic acid base aliphatic polyester, and C is polyisocyanates.In formula, m=2 ~ 100, preferably 10 ~
50；N represents number of branches, n=2 ~ 20, and preferably 2 ~ 10.
Described polylactic acid base aliphatic polyester, for L-type lactide and trimethylene carbonate, Acetic acid, hydroxy-, bimol. cyclic ester, poly-3-hydroxyl alkane
Acid esters, polycaprolactone or the binary of Polyethylene Glycol copolymerization formation or multiple copolymer.Its number-average molecular weight is 5 × 103~2×
105G/mol, preferably 1 × 104~5×104G/mol, molecular weight distribution index is 1.2 ~ 3.5.
Described polyhydric alcohol, for BDO, polyether polyol, glycerol, tetramethylolmethane, dipentaerythritol or other
One in polyhydric alcohol.Its number-average molecular weight is 1 × 103~1×104G/mol, preferably 3 × 103~6×103g/mol。
Described polyisocyanates, for diisocyanate, triisocyanate or their modified body.Wherein, diisocyanate
Including: aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate or its mixture；Triisocyanate
It it is then triphenylmethane triisocyanate.Wherein, aliphatic diisocyanate include isophorone diisocyanate, 1,6-six is sub-
Methyl diisocyanate or 4,4-bicyclo-ethyl methane diisocyanate；Aromatic diisocyanate includes toluene diisocynate
Ester, 4,4 methyl diphenylene diisocyanates or XDI.
The present invention also provides for the preparation method of described Biodegradable Shape-Memory Polyurethane, concretely comprises the following steps:
(1) linear or cladodification polylactic acid base aliphatic polyester are dissolved in the organic solvent through processing except water, add catalyst
And polyisocyanates, reactive polymeric in atmosphere of inert gases；
(2) reaction solution is poured into have in the middle of the mould of flat surface, be placed in solution evaporation under uniform temperature to dry；Then at
Ripening under high temperature, obtains Biodegradable Shape-Memory Polyurethane thin film.
In step (1), described organic solvent is benzene,toluene,xylene, DMF (DMF), tetrahydrochysene furan
Mutter any one or more in (THF), normal hexane, chloroform, ethyl acetate, ketone, ethyl ketone, dichloromethane.
In step (1), described catalyst is stannous octoate, stannous chloride, stannic chloride, Tin dibromide., zinc chloride, lactic acid
One or more in zinc, stannum oxide, zinc oxide, zirconium oxide.The addition of catalyst is the 1/5000 ~ 1/ of monomer gross mass
500, preferably 1/5000 ~ 1/1000.
In step (1), described polyisocyanates is diisocyanate, triisocyanate or their modified body.Two isocyanides
Acid esters is aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate or its mixture, triisocyanate
It it is then triphenylmethane triisocyanate.Wherein, described aliphatic diisocyanate include isophorone diisocyanate, 1,6-
Hexamethylene diisocyanate or 4,4-bicyclo-ethyl methane diisocyanate；Aromatic diisocyanate includes toluene diisocyanate
Acid esters, 4,4 methyl diphenylene diisocyanates or XDI.
In step (1), described polymerization temperature is 30 ~ 90 DEG C, preferably 50 ~ 80 DEG C；Polymerization time is 0.5 ~ 6h, preferably 2 ~
4h。
In step (2), described solvent volatilization temperature is 30 ~ 70 DEG C, preferably 40 ~ 60 DEG C；Curing temperature is 100 ~ 200
DEG C, preferably 120 ~ 150 DEG C；Curing time is 1 ~ 20h, preferably 4 ~ 10h.
Present invention also offers the application of described Biodegradable Shape-Memory Polyurethane, it can be wide as bio-medical material
General it is applied to biomedical sector, such as operation suture thread, Thermosensitive Material Used for Controlled Releasing of Medicine, fracture fixation device etc..
In the present invention, above-mentioned optimum condition on the basis of compound common sense in the field can combination in any, the present invention
Each preferred embodiment.
The raw material of the present invention and reagent are the most commercially.
The present invention, in degradable poly lactyl aliphatic polyester matrix, introduces diisocyanate as chain extender, preparation
Obtain polyurethane material.On the one hand in polyester material, physics and chemical crosslinking point are added so that the fixed rate of material and returning
Multiple rate increases.Material deformation rate is about 300%, and shape fixed rate is 97-100%, and shape recovery rate is 95-100%.The opposing party
Face improves biocompatibility and the degradation property of polyurethane material.
It is big that material of the present invention has deformation recovery power, and recovery temperature is low, remembers reproducible advantage, has biology simultaneously
The compatibility and the advantage of biological degradability.By regulation cladodification or the chemical constitution of linear polylactic acid base aliphatic polyester, controlled
Recovery temperature processed is near human body temperature, and the size of scalable restoring force, implants medical material neck at Minimally Invasive Surgery and human body
Territory has broad application prospects.
Accompanying drawing explanation
The DSC spectrogram of Fig. 1 Biodegradable Shape-Memory Polyurethane: sample starts to be warming up to 200 DEG C with 10 DEG C/min from room temperature,
Isothermal 1min is to eliminate thermal history；Then it is cooled to 0 DEG C with 50 DEG C/min, then is warming up to 200 DEG C with 10 DEG C/min.Result is taken from
Second time heating curve.
The stress-strain diagram of Fig. 2 Biodegradable Shape-Memory Polyurethane.
The shape memory return curve of Fig. 3 Biodegradable Shape-Memory Polyurethane: with the heating rate of 3 DEG C/min from room temperature
Rise to 60 DEG C.
The shape memory of Fig. 4 Biodegradable Shape-Memory Polyurethane replys photo.
Detailed description of the invention
Further illustrating the present invention by embodiment below, but the present invention is not intended to be limited thereto, the raw material in embodiment is equal
For conventional commercial product, wherein:
Biodegradable Shape-Memory Polyurethane material prepared by the present invention, common by Fourier transform infrared spectroscopy (FTIR), nuclear-magnetism
The hydrogen that shakes spectrum (1H NMR) determines that its chemical composition, differential scanning calorimetry (DSC) measure its hot property, and universal tensile testing machine is surveyed
Its mechanical property fixed, DMA and TMA determines its shape-memory properties.
Embodiment 1
(1) it is 3.0 × 10 by 5.40g molecular weight4Three arm PPO-PLLA-TMC-GA copolymer (PLLA, TMC, GA tri-of g/mol
The mol ratio planting monomer is 75/20/5) it is dissolved in 100ml dry toluene solvent, add 0.07g stannous octoate and 33mg hexichol
Dicyclohexylmethane diisocyanate (MDI)；Reactive polymeric in nitrogen atmosphere, polymer temperature is 50 DEG C, reacts 1.5h.Reaction terminates
After, reaction solution is poured in quartz box, be placed in 70 DEG C of baking ovens solution evaporation is the most dry, be ripening 1.5h at 120 DEG C,
To Biodegradable Shape-Memory Polyurethane thin film.
(2) Fig. 1 is the DSC spectrogram of gained polyurethane material.The glass transition temperature of this sample (TG) it is 45.3 DEG C,
There is no crystalline melting peak.To largely reduce embedded material in the forfeiture principle of crystallizing power causes late inflammatory to react wind
Danger.
(3) Fig. 2 is the stress-strain diagram of polyurethane material.The mechanical performance of polyurethane is real according to GB/T 528-1998
Executing, style makes 2-type dumbbell shaped batten, length 20mm, width 4mm.5 parallel battens of each sample test.Obtain style
Hot strength 49.9MPa, Young's modulus is 1829MPa, and elongation percentage is 322%.
(4) Fig. 3 is the return curve of polyurethane material.The starting back temperature of this sample (TI) it is 37.3 DEG C, more connects
Person of modern times's temperature, deformation-recovery rate is up to 100%.
(5) Fig. 4 is the deformation recovery process photo of polyurethane material.It is fixed to helical form, after cooling after being heated by material
Shape is fixed, and makes its deformation recovery at 48.0 DEG C.Only need 22s material can return back to original shape.
Embodiment 2
It is 1.3 × 10 by 5.33g molecular weight5The PLLA-TMC-GA terpolymer of g/mol be (tri-kinds of monomers of PLLA, TMC, GA
Mol ratio is 90/5/5) it is dissolved in 100ml dry toluene solvent, add 0.16g stannous octoate and 25mg diphenyl methane two
Isocyanates (MDI).Polymerization and maturing process are as described in Example 1.Gained polyurethane material glass transition temperature is 47.2
DEG C, nodeless mesh behavior.Hot strength is 49.6MPa, and Young's modulus is 1743MPa, and elongation percentage is 305%.Starting back temperature
(TI) being 40.6 DEG C, deformation-recovery rate is 100%.
Embodiment 3
It is 1.1 × 10 by 5.33g molecular weight5PLLA-TMC bipolymer (the mol ratio of two kinds of monomers of PLLA, TMC of g/mol
It is 90/10) it is dissolved in 100ml dry toluene solvent, add 0.18g stannous octoate and 23mg toluene di-isocyanate(TDI) (TDI).
Polymerization and maturing process are as described in Example 1.Gained polyurethane material glass transition temperature is 53.2 DEG C, and crystallizing power is more weak
(ΔH m= 1.2 J/g).Hot strength is 50.3MPa, and Young's modulus is 1796MPa, and elongation percentage is 128%.Starting back temperature
Degree (TI) being 41.6 DEG C, deformation-recovery rate is 98%.
Embodiment 4
It is 5.0 × 10 by 5.33g molecular weight4PLLA-PCL bipolymer (the mol ratio of two kinds of monomers of PLLA, PCL of/mol
It is 80/20) it is dissolved in 100ml dry toluene solvent, add 0.16g stannous octoate and 40mg toluene di-isocyanate(TDI) (TDI).
Polymerization and maturing process are as described in Example 1.Gained polyurethane material glass transition temperature is 36.6 DEG C, and crystallizing power is stronger
(ΔH m= 23.4 J/g).Hot strength is 55.3MPa, and Young's modulus is 1679MPa, and elongation percentage is 320%.Starting back temperature
Degree (TI) being 28.6 DEG C, deformation-recovery rate is 98%.
Embodiment 5
It is 7.0 × 10 by 5.33g molecular weight4PLLA-PCL bipolymer (the mol ratio of two kinds of monomers of PLLA, PCL of/mol
It is 80/20) it is dissolved in 100ml dry toluene solvent, add 0.16g stannous octoate and 35mg methyl diphenylene diisocyanate
(MDI).Polymerization and maturing process are as described in Example 1.Gained polyurethane material glass transition temperature is 41.7 DEG C, crystal energy
Relatively strong (the Δ of powerH m= 11.4 J/g).Hot strength is 35.3MPa, and Young's modulus is 1754MPa, and elongation percentage is 300%.Initial
Recovery temperature (TI) being 33.6 DEG C, deformation-recovery rate is 100%.
Embodiment 6
It is 1.5 × 10 by 5.33g molecular weight4(tetramethylolmethane causes the four arm PLLA-PEG bipolymers of/mol, PLLA, PCL
The mol ratio of two kinds of monomers is 80/20) it is dissolved in 100ml dry toluene solvent, add 0.16g stannous octoate and 45mg hexichol
Dicyclohexylmethane diisocyanate (MDI).Polymerization and maturing process are as described in Example 1.Gained polyurethane material glass transition temperature
Degree is 26.7 DEG C, the relatively strong (Δ of crystallizing powerH m= 27.4 J/g).Hot strength is 31.3MPa, and Young's modulus is 1549MPa,
Elongation percentage is 500%.Starting back temperature (TI) being 20.6 DEG C, deformation-recovery rate is 100%.
Embodiment 7
It is 4.2 × 10 by 5.33g molecular weight4The four arm PLLA-TMC-GA copolymers of/mol (tetramethylolmethane causes, PLLA, TMC,
The mol ratio of tri-kinds of monomers of GA is 75/10/15) be dissolved in 100ml dry toluene solvent, add 0.16g stannous octoate and
50mg toluene di-isocyanate(TDI) (TDI).Polymerization and maturing process are as described in Example 1.Gained polyurethane material glass transition
Temperature is 47.0 DEG C, nodeless mesh phase.Hot strength is 73.1MPa, and Young's modulus is 2245MPa, and elongation percentage is 350%.Initiate back
Rewarming degree (TI) being 35.2 DEG C, deformation-recovery rate is 100%.
Embodiment 8
It is 5.2 × 10 by 5.33g molecular weight4(glycerol causes the three arm PLLA-TMC-GA copolymers of/mol, PLLA, TMC, GA
The mol ratio of three kinds of monomers is 75/10/15) it is dissolved in 100ml dry toluene solvent, add 0.16g stannous octoate and 45mg
Toluene di-isocyanate(TDI) (TDI).Polymerization and maturing process are as described in Example 1.Gained polyurethane material glass transition temperature
It is 47.0 DEG C, nodeless mesh phase.Hot strength is 64.1MPa, and Young's modulus is 1740MPa, and elongation percentage is 3870%.Starting back
Temperature (TI) being 34.2 DEG C, deformation-recovery rate is 100%.
Embodiment 9
It is 4.5 × 10 by 5.33g molecular weight4The six arm PLLA-TMC-GA copolymers of/mol (dipentaerythritol, PLLA, TMC,
The mol ratio of tri-kinds of monomers of GA is 75/10/15) be dissolved in 100ml dry toluene solvent, add 0.16g stannous octoate and
50mg toluene di-isocyanate(TDI) (TDI).Polymerization and maturing process are as described in Example 1.Gained polyurethane material glass transition
Temperature is 49.0 DEG C, nodeless mesh phase.Hot strength is 61.3MPa, and Young's modulus is 1590MPa, and elongation percentage is 3026%.Initial
Recovery temperature (TI) being 41.2 DEG C, deformation-recovery rate is 100%.
From above-described embodiment it can be seen that with line style or cladodification polylactic acid base aliphatic polyester as matrix, prepare degradable
Shape memory polyurethane material.Its starting back temperature is closer to human body temperature, and response rate is higher, is 98% ~ 100%.Logical
Overregulate the chemical constitution of material, material can be made to obtain higher hot strength and elongation at break.In principle, may conform to biology
The serviceability requirement of medical material.
Claims (10)
1. a Biodegradable Shape-Memory Polyurethane material, it is characterised in that be based on linear or cladodification polylactic acid base aliphatic
Polyester, this material with the flexible molecule chain of polylactic acid base aliphatic polyester for can anti-phase, with the alcohol of polyisocyanates Yu polyester
Carbamate, copolymer crystallization and chemical crosslinking point that hydroxyl is formed are fixing phase, and its structural formula is:
Wherein, A is polyhydric alcohol, and B is polylactic acid base aliphatic polyester, and C is polyisocyanates, in formula, m=2 ~ 100；N represents branch
Number, n=2 ~ 20.
2. Biodegradable Shape-Memory Polyurethane material as claimed in claim 1, it is characterised in that described polylactic acid base aliphatic
Polyester is L-type lactide and trimethylene carbonate, Acetic acid, hydroxy-, bimol. cyclic ester, poly-3-hydroxyalkanoate, polycaprolactone or Polyethylene Glycol copolymerization
The binary formed or multiple copolymer.
3. Biodegradable Shape-Memory Polyurethane material as claimed in claim 1, it is characterised in that described polylactic acid base aliphatic
Polyester, its number-average molecular weight is 5 × 103~2×105G/mol, molecular weight distribution index is 1.2 ~ 3.5.
4. Biodegradable Shape-Memory Polyurethane material as claimed in claim 1, it is characterised in that be used for causing synthesis cladodification type
The polyhydric alcohol of polylactic acid base aliphatic polyester is 1,4-butanediol, polyether polyol, glycerol, tetramethylolmethane, dimerization Ji Wusi
One in alcohol or other polyhydric alcohol, its number-average molecular weight is 1 × 103~1×104g/mol。
5. Biodegradable Shape-Memory Polyurethane material as claimed in claim 1, it is characterised in that described polyisocyanates is two
Isocyanates, triisocyanate and their modified body；Wherein, diisocyanate is aliphatic diisocyanate, aromatic series two
Isocyanates, alicyclic diisocyanate or its mixture；Triisocyanate is triphenylmethane triisocyanate.
6. Biodegradable Shape-Memory Polyurethane material as claimed in claim 5, it is characterised in that described aliphatic two Carbimide.
Ester is isophorone diisocyanate, 1,6-hexamethylene diisocyanate or 4,4-bicyclo-ethyl methane diisocyanate；Virtue
Fragrant (cyclo) aliphatic diisocyanates is toluene di-isocyanate(TDI), 4,4 methyl diphenylene diisocyanates or XDI.
7. a preparation method for the Biodegradable Shape-Memory Polyurethane material as described in one of claim 1-6, its feature exists
In, comprise the concrete steps that:
(1) linear or cladodification polylactic acid base aliphatic polyester are dissolved in the organic solvent through processing except water, add catalyst
And polyisocyanates, the addition of catalyst is the 1/5000 ~ 1/500 of reactant gross mass；React in atmosphere of inert gases
Polymerization, polymerization temperature is 30 ~ 90 DEG C, and polymerization time is 0.5 ~ 6h；
(2) reaction solution is poured into have in the middle of the mould of flat surface, be placed in the environment of temperature is 30 ~ 70 DEG C and solution is waved
Send to do；Ripening 1 ~ 20h at 100 ~ 200 DEG C, obtains Biodegradable Shape-Memory Polyurethane thin film again.
8. preparation method as claimed in claim 7, it is characterised in that described organic solvent is benzene,toluene,xylene, N, N-
Any one in dimethylformamide, oxolane, normal hexane, chloroform, ethyl acetate, ketone, ethyl ketone, dichloromethane
Or it is multiple.
9. preparation method as claimed in claim 7, it is characterised in that described catalyst is stannous octoate, stannous chloride, chlorine
Change one or more in stannum, Tin dibromide., zinc chloride, zinc lactate, stannum oxide, zinc oxide, zirconium oxide.
10. Biodegradable Shape-Memory Polyurethane material as claimed in claim 1 is as the application of bio-medical material.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN110123467A (en) * | 2019-05-21 | 2019-08-16 | 尤美医疗科技(大连)有限公司 | Gear division correction stealth facing and its application method with shape memory function |
| CN111848918A (en) * | 2020-06-28 | 2020-10-30 | 梅其勇 | Biodegradable polyurethane for intravascular stent and synthesis method thereof |
| CN112759737A (en) * | 2019-11-04 | 2021-05-07 | 中国石油化工股份有限公司 | Triple shape memory polymer and preparation method thereof |
| CN113527627A (en) * | 2021-08-18 | 2021-10-22 | 中国科学院海洋研究所 | Polylactic acid polycarbonate-based polyurethane with self-repairing function and preparation method and application thereof |
| CN115105632A (en) * | 2022-07-15 | 2022-09-27 | 重庆大学 | Application of polylactic acid and shape memory polyurethane material compound in preparation of bone repair material |
| CN115154671A (en) * | 2022-07-15 | 2022-10-11 | 重庆大学 | Composite of polylactic acid and shape memory polyurethane material |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108264623A (en) * | 2018-01-23 | 2018-07-10 | 中国科学院长春应用化学研究所 | A kind of polyester polyurethane shape-memory material and preparation method thereof |
| CN110123467A (en) * | 2019-05-21 | 2019-08-16 | 尤美医疗科技(大连)有限公司 | Gear division correction stealth facing and its application method with shape memory function |
| CN112759737A (en) * | 2019-11-04 | 2021-05-07 | 中国石油化工股份有限公司 | Triple shape memory polymer and preparation method thereof |
| CN112759737B (en) * | 2019-11-04 | 2022-07-12 | 中国石油化工股份有限公司 | Triple shape memory polymer and preparation method thereof |
| CN111848918A (en) * | 2020-06-28 | 2020-10-30 | 梅其勇 | Biodegradable polyurethane for intravascular stent and synthesis method thereof |
| CN113527627A (en) * | 2021-08-18 | 2021-10-22 | 中国科学院海洋研究所 | Polylactic acid polycarbonate-based polyurethane with self-repairing function and preparation method and application thereof |
| CN115105632A (en) * | 2022-07-15 | 2022-09-27 | 重庆大学 | Application of polylactic acid and shape memory polyurethane material compound in preparation of bone repair material |
| CN115154671A (en) * | 2022-07-15 | 2022-10-11 | 重庆大学 | Composite of polylactic acid and shape memory polyurethane material |
| CN115154671B (en) * | 2022-07-15 | 2023-06-16 | 重庆大学 | Polylactic acid and shape memory polyurethane material compound |
| CN115105632B (en) * | 2022-07-15 | 2023-12-01 | 重庆大学 | Application of polylactic acid and shape memory polyurethane material compound in preparation of bone repair material |
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